EP1564208B1 - Process for producing methionine - Google Patents
Process for producing methionine Download PDFInfo
- Publication number
- EP1564208B1 EP1564208B1 EP04003353A EP04003353A EP1564208B1 EP 1564208 B1 EP1564208 B1 EP 1564208B1 EP 04003353 A EP04003353 A EP 04003353A EP 04003353 A EP04003353 A EP 04003353A EP 1564208 B1 EP1564208 B1 EP 1564208B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methionine
- filtrate
- temperature
- process according
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 title claims abstract description 49
- 229930182817 methionine Natural products 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000706 filtrate Substances 0.000 claims description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 12
- 239000011736 potassium bicarbonate Substances 0.000 claims description 12
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 12
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- SBKRXUMXMKBCLD-UHFFFAOYSA-N 5-(2-methylsulfanylethyl)imidazolidine-2,4-dione Chemical compound CSCCC1NC(=O)NC1=O SBKRXUMXMKBCLD-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 238000009738 saturating Methods 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 108010085203 methionylmethionine Proteins 0.000 abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 12
- ZYTPOUNUXRBYGW-UHFFFAOYSA-N methionyl-methionine Chemical compound CSCCC(N)C(=O)NC(C(O)=O)CCSC ZYTPOUNUXRBYGW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 108010016626 Dipeptides Proteins 0.000 description 3
- ZYTPOUNUXRBYGW-YUMQZZPRSA-N Met-Met Chemical compound CSCC[C@H]([NH3+])C(=O)N[C@H](C([O-])=O)CCSC ZYTPOUNUXRBYGW-YUMQZZPRSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 150000002741 methionine derivatives Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- -1 hydantoin compound Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/12—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by hydrolysis, i.e. solvolysis in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/30—Extraction; Separation; Purification by precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/34—Extraction; Separation; Purification by filtration, ultrafiltration or reverse osmosis
Definitions
- the present invention refers to a process to quickly hydrolyze the dipeptide methionyl-methionine.
- the hydrolysis reaction might be carried out in connection with a process for producing methionine for increasing the final yield of the desired end product methionine.
- hydrolysis or dipeptide cleavage reaction is, however, subject to various imponderabilities.
- the by-products may interfere negatively with the carbonization reaction taking place during the final step of methionine formation by crystallization at lower pH values.
- the prior art EP 839 804 suggests to hydrolyze methionine dimers at temperatures within a range of 150 to 200°C, preferably at 170°C to 190°C. It is stated that at temperatures above 200°C the resulting methionine might suffer from thermal degradation and that still further materials of the reaction equipment corrode at temperatures above 200°C.
- proteins are degraded to peptides and/or amino acids in supercritical water (that is above 355°C with a pressure of at least 22 MPa) or highpressure hot water near the critical point.
- supercritical water that is above 355°C with a pressure of at least 22 MPa
- highpressure hot water near the critical point.
- highly corrosion resistant and hence extremely expensive equipment would become necessary.
- undesired side reactions and resulting by-products are expected to occur at such high temperatures.
- the end product methionine will be subject to thermal degradation.
- the dipeptide cleavage i.e. the hydrolysis of methionyl-methionine
- hydrolysis typically occurs slowly at temperatures below 200°C, hence such temperature ranges would seem unsuitable for industrially applicable processes since the hydrolysis takes too long from an economic point of view.
- supercritical water presents the above-mentioned drawbacks, due to increased side reactions and the risk of thermal degradation of the desired end product methionine.
- the present invention is to be applied to a process for producing methionine which comprises hydrolyzing 5- ( ⁇ -methylmercaptoethyl)hydantoin by using at least one member selected from potassium carbonate, potassium bicarbonate and potassium hydroxide, then precipitating methionine out of the reaction liquid under applied pressure of carbon dioxide, separating and collecting the methionine to leave a filtrate, and recycling, for reusing, the filtrate to the step of the hydrolysis of the hydantoin compound.
- the conditions for the above-mentioned steps (a) and (b) are not particularly limited.
- known methods for example as described in U.S. Pat. No. 4,069,251 and U.S. Pat. No. 4,303,621 , can be used.
- 5-( ⁇ -methylmercaptoethyl)hydantoin is hydrolyzed by using potassium carbonate and/or potassium bicarbonate, the ratio between the hydantoin and the alkali (potassium carbonate and/or potassium bicarbonate) possibly being between 1:1 and 1:5, at an approximate temperature of from 120°C to 220°C, then carbon dioxide is fed to the reaction system to saturate the methionine-containing solution and thereby to precipitate methionine, and the methionine thus precipitated is separated by conventional methods of solid-liquid separation.
- part of the first filtrate left behind in step (b) can be returned to the circulatory system as it is or after it is concentrated, and recycled to and reused in step (a). Recycling and reusing all the filtrate in this way over a long period would undesirably accumulate impurities and decomposition products in the system, which would reduce the purity of methionine produced. Therefore, in order to avoid the potential risk of accumulation of impurities and colored components in the system, it has been recommended to remove the filtrate according to necessity, for example in a definite proportion, out of the system (the so-called partial purging).
- the second filtrate left behind in step (d) can be returned to step (a), although it can be discharged economically and environmental-friendly.
- the amount of the filtrate to be partly purged is not particularly limited and may vary depending on the amounts of impurities and colored substances contained in the first filtrate, but it is preferably about 3-20%, more preferably 3-10% of the total amount of the first part of the first filtrate if it is present and the second filtrate if it is recycled and reused.
- the second part of the first filtrate can be heat-treated as it is or after it is concentrated.
- the filtrate to be heat-treated usually contains about 90-160 g/l of potassium, about 30-100 g/l of methionine and about 5-60 g/l of methionyl-methionine.
- the concentration of potassium referred to in the present invention may be determined by titration.
- the temperature of the heat treatment (step (d)) of the second part of the first filtrate is particularly critical and falls within a range of 210°C-280°C, preferably within an range of 220°C-280°C, more preferably of from 220°C-260°C.
- the dimer can be rapidly hydrolyzed at a temperature higher than 200°C, for a time period short enough to prevent the thermal degradation of methionine.
- the period of time for heat treatment also is particularly critical and may vary depending an the concentration of methionine dimer in the second part of the first filtrate. It is within a range of 20 s to 200 s, preferably within a range of 20 s to 150 s, more preferably within a range of 20 s to 100 s, and most preferably within a range of 20 s to 60 s. With longer periods of time of heat treatment the methionine would suffer thermal degradation.
- step (d) should be carried out at a pressure above the vapor pressure of the water at the temperature employed.
- the pressure of carbon dioxide gas to be applied in terms of gauge pressure (the amount by which the total absolute pressure exceeds the ambient atmospheric pressure), is not critical, but usually ranges from about 1.5-20 bar, preferably about 2-6 bar. When the pressure of carbon dioxide gas is less than about 1.5 bar the recoveries of methionine and potassium bicarbonate tend to be insufficient; on the other hand, even when the pressure is increased over about 20 bar, sometimes no further improvement in these recoveries is observed.
- the precipitation is preferably carried out at low temperatures.
- the precipitation temperature particularly at the time of completion of the precipitation, preferably falls within the range of from about -10°C to about +40°C, more preferably from about 0°C to about +20°C, still more preferably in the neighborhood of about 0°C to about +5°C.
- a concentrating operation can be conducted in any step, and is preferably conducted before and/or after the heat treatment of the second part of the first filtrate.
- the conditions of the concentrating operation are not particularly limited so long as they do not cause substantial thermal degradation of methionine, therefore, various conditions may be adopted in principle.
- the temperature of the concentrating operation preferably falls within the range of from about 50°C to about 160°C, more preferably from about 50°C to about 140°C
- the pressure of the concentrating operation preferably falls within the range of from 0 to about 2 bar in terms of absolute pressure or a lower pressure, more preferably from 0 to about 1.5 bar in terms of absolute pressure.
- the concentrating operation can be conducted simultaneously in combination with the heat-treating operation in step (d).
- the concentrating operation would naturally be conducted under the claimed operation conditions of heat treatment, i.e., above 200°C for a time period of less than 200 s.
- the concentrating operation and the heat-treating operation are preferably conducted independently of each other.
- treating the second part of the first filtrate in the manner described above enables to remove the impurities and colored components present in the circulatory system to the outside of the system while effectively recovering methionine and potassium bicarbonate contained in the filtrate.
- Step (d) of treating second part of the first filtrate in the present invention can be conducted either batchwise or continuously.
- methionine dimer present in the system can be utilized effectively and resultantly the yield of methionine is improved, the accumulation of impurities and colored substances in the reaction system is avoided, and methionine and potassium bicarbonate can be recovered easily and with good efficiency.
- the present invention is of a great industrial value.
- the process according to the invention is suited to increase the yield of the final end product methionine during a process for producing methionine. Due to significantly shorter reaction times (residence times of from 20 s to 200 s) the facilities consisting of special materials, can be constructed smaller, making the process most economic.
- the hydrolysis (step (d)) of the present invention can be carried out without any addition of a solvent.
- the hydrolysis of the present invention can be carried out directly with the methionine-mother liquor as starting material.
- the reaction is catalyzed by either acid or base. Suitable catalyzation can be achieved by adding KOH to adjust the pH to values about 14. Within the claimed temperature and pressure ranges, there occur no bothering side products during the hydrolysis reaction in view of the final carbonization reaction.
- the reactant solution is suck from the glass container 101 by the HPLC pump 102.
- the volume flow is regulated by the number of rotations of the HPLC pump (FIC 102.1).
- the pressure at the pressure side of the pump is regulated by the pressure control valve (PIC S+ 102.2).
- An interlock (S+) stops the pump, if the pressure exceeds 40 MPa.
- the coiled tubing reactor consists of 6 m capillary of 3x1 mm, wrapped up a tube with an outer diameter of 168 mm filled with isolation material.
- the capillary wrapped up this tube is incorporated in a heat sleeve with a nominal power of 2 kW.
- thermocouples TI 103.1 and 103.2
- TI S+ 103.2 over-temperature safety device
- thermocouple Downstream the reactor a T-piece can be found, in which a thermocouple is screwed in (TIC 103.3). Therewith the temperature of the solution at the outlet of the reactor 103 is measured. This measured value is the actual value of the temperature control.
- a further thermocouple TI 103.4
- TI 103.4 thermocouple
- the pressure of the whole facility is shown by the pressure gauge downstream the cryostat device (PI 104.1).
- the reactant solution is set free by the pressure control valve and collected by the empty washing bottle 105.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Biophysics (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
- The present invention refers to a process to quickly hydrolyze the dipeptide methionyl-methionine. The hydrolysis reaction might be carried out in connection with a process for producing methionine for increasing the final yield of the desired end product methionine.
- Processes for producing methionine are well known in the art and are for example described in
US 4,069,251 . During processes for producing methionine, one of the most prominent side products is the dipeptide methionyl-methionine. For optimizing the yield of the methionine forming reaction, one might benefit from the hydrolysis of this dipeptide. That is, due the cleavage of methionyl-methionine, resulting in two methionine molecules, a higher yield of the final product can be obtained. - The hydrolysis or dipeptide cleavage reaction is, however, subject to various imponderabilities. One has to bear in mind that during the hydrolysis by-products might be formed. The by-products may interfere negatively with the carbonization reaction taking place during the final step of methionine formation by crystallization at lower pH values.
- The prior art
EP 839 804 - According to
EP 1 312 611 , proteins are degraded to peptides and/or amino acids in supercritical water (that is above 355°C with a pressure of at least 22 MPa) or highpressure hot water near the critical point. However, at such high temperatures, highly corrosion resistant and hence extremely expensive equipment would become necessary. Furthermore, undesired side reactions and resulting by-products are expected to occur at such high temperatures. Still further, the end product methionine will be subject to thermal degradation. - The dipeptide cleavage, i.e. the hydrolysis of methionyl-methionine, typically occurs slowly at temperatures below 200°C, hence such temperature ranges would seem unsuitable for industrially applicable processes since the hydrolysis takes too long from an economic point of view. On the other hand, supercritical water presents the above-mentioned drawbacks, due to increased side reactions and the risk of thermal degradation of the desired end product methionine.
- Thus, there is a strong need to provide an economically viable process for hydrolyzing methionyl-methionine at reasonable rates, while undesired side reactions and the degradation of the end product are avoided. Simultaneously, the facilities consisting of highly corrosion-resistant and thus expensive materials should be kept small.
- It has now surprisingly been found that the hydrolysis of methionyl-methionine can be carried out with significantly higher space-time yields (i.e. at low reaction volumes) by a process as set out in the claims.
- According to the present invention, there is provided a process for producing methionine which comprises the steps of:
- a) adding at least one compound selected from potassium carbonate, potassium bicarbonate and potassium hydroxide to a solution containing 5- (β-methylmercaptoethyl)hydantoin to hydrolyze the 5- (β-methylmercaptoethyl)hydantoin to obtain a solution containing methionine,
- b) saturating the solution containing methionine with carbon dioxide to precipitate the methionine, and separating the precipitated methionine while leaving a first filtrate behind,
- c) dividing the first filtrate into a first part and a second part returning the first part to step (a), and transferring the second part to step (d), wherein the first part of the first filtrate can be absent,
- d) heating the second part of the first filtrate to a temperature from 210°C to 280°C for a residence time between 20 and 200 seconds and at a pressure above the vapor pressure of the water at the temperature employed, and saturating the heat-treated filtrate with carbon dioxide to precipitate the methionine and potassium bicarbonate, and separating the precipitated methionine and potassium bicarbonate while leaving a second filtrate behind, and
- e) discharging the second filtrate or returning it to step (a).
- According to the improved process of the present invention, significantly higher space-time yields can be achieved, whereby the economic efficiency of the process can be guaranteed.
- The present invention is to be applied to a process for producing methionine which comprises hydrolyzing 5- (β-methylmercaptoethyl)hydantoin by using at least one member selected from potassium carbonate, potassium bicarbonate and potassium hydroxide, then precipitating methionine out of the reaction liquid under applied pressure of carbon dioxide, separating and collecting the methionine to leave a filtrate, and recycling, for reusing, the filtrate to the step of the hydrolysis of the hydantoin compound.
- In the present invention, the conditions for the above-mentioned steps (a) and (b) are not particularly limited. As to the conditions for steps (a) and (b), known methods, for example as described in
U.S. Pat. No. 4,069,251 andU.S. Pat. No. 4,303,621 , can be used. In such a method, 5-(β-methylmercaptoethyl)hydantoin is hydrolyzed by using potassium carbonate and/or potassium bicarbonate, the ratio between the hydantoin and the alkali (potassium carbonate and/or potassium bicarbonate) possibly being between 1:1 and 1:5, at an approximate temperature of from 120°C to 220°C, then carbon dioxide is fed to the reaction system to saturate the methionine-containing solution and thereby to precipitate methionine, and the methionine thus precipitated is separated by conventional methods of solid-liquid separation. - In the present invention, part of the first filtrate left behind in step (b) can be returned to the circulatory system as it is or after it is concentrated, and recycled to and reused in step (a). Recycling and reusing all the filtrate in this way over a long period would undesirably accumulate impurities and decomposition products in the system, which would reduce the purity of methionine produced. Therefore, in order to avoid the potential risk of accumulation of impurities and colored components in the system, it has been recommended to remove the filtrate according to necessity, for example in a definite proportion, out of the system (the so-called partial purging).
- In the present invention, the second filtrate left behind in step (d) can be returned to step (a), although it can be discharged economically and environmental-friendly.
- In the present invention, the amount of the filtrate to be partly purged (second part of the first filtrate in step (c)) is not particularly limited and may vary depending on the amounts of impurities and colored substances contained in the first filtrate, but it is preferably about 3-20%, more preferably 3-10% of the total amount of the first part of the first filtrate if it is present and the second filtrate if it is recycled and reused. The second part of the first filtrate can be heat-treated as it is or after it is concentrated. The filtrate to be heat-treated usually contains about 90-160 g/l of potassium, about 30-100 g/l of methionine and about 5-60 g/l of methionyl-methionine. The concentration of potassium referred to in the present invention may be determined by titration.
- The temperature of the heat treatment (step (d)) of the second part of the first filtrate is particularly critical and falls within a range of 210°C-280°C, preferably within an range of 220°C-280°C, more preferably of from 220°C-260°C. The dimer can be rapidly hydrolyzed at a temperature higher than 200°C, for a time period short enough to prevent the thermal degradation of methionine.
- The period of time for heat treatment also is particularly critical and may vary depending an the concentration of methionine dimer in the second part of the first filtrate. It is within a range of 20 s to 200 s, preferably within a range of 20 s to 150 s, more preferably within a range of 20 s to 100 s, and most preferably within a range of 20 s to 60 s. With longer periods of time of heat treatment the methionine would suffer thermal degradation.
- It should further be noted, that step (d) should be carried out at a pressure above the vapor pressure of the water at the temperature employed.
- The pressure of carbon dioxide gas to be applied, in terms of gauge pressure (the amount by which the total absolute pressure exceeds the ambient atmospheric pressure), is not critical, but usually ranges from about 1.5-20 bar, preferably about 2-6 bar. When the pressure of carbon dioxide gas is less than about 1.5 bar the recoveries of methionine and potassium bicarbonate tend to be insufficient; on the other hand, even when the pressure is increased over about 20 bar, sometimes no further improvement in these recoveries is observed.
- The precipitation is preferably carried out at low temperatures. The precipitation temperature, particularly at the time of completion of the precipitation, preferably falls within the range of from about -10°C to about +40°C, more preferably from about 0°C to about +20°C, still more preferably in the neighborhood of about 0°C to about +5°C.
- In the present invention, a concentrating operation can be conducted in any step, and is preferably conducted before and/or after the heat treatment of the second part of the first filtrate. The conditions of the concentrating operation are not particularly limited so long as they do not cause substantial thermal degradation of methionine, therefore, various conditions may be adopted in principle. However, in consideration of the energy efficiency and the corrosion of the materials of the reaction equipment, the temperature of the concentrating operation preferably falls within the range of from about 50°C to about 160°C, more preferably from about 50°C to about 140°C, and the pressure of the concentrating operation preferably falls within the range of from 0 to about 2 bar in terms of absolute pressure or a lower pressure, more preferably from 0 to about 1.5 bar in terms of absolute pressure.
- In the present invention, the concentrating operation can be conducted simultaneously in combination with the heat-treating operation in step (d). In such a case, the concentrating operation would naturally be conducted under the claimed operation conditions of heat treatment, i.e., above 200°C for a time period of less than 200 s. However, it would not be preferable from the viewpoint of energy efficiency and other factors to adopt the relatively severe operation conditions in heat treatment for the purpose of concentrating operation. Therefore, the concentrating operation and the heat-treating operation are preferably conducted independently of each other.
- According to the present invention, treating the second part of the first filtrate in the manner described above enables to remove the impurities and colored components present in the circulatory system to the outside of the system while effectively recovering methionine and potassium bicarbonate contained in the filtrate.
- Step (d) of treating second part of the first filtrate in the present invention can be conducted either batchwise or continuously.
- As described above, according to the present invention, merely by using a method which comprises heat-treating the second part of the first filtrate taken from the conventional process for producing methionine, and precipitating methionine out of the heat-treated filtrate under applied pressure of carbon dioxide gas, methionine dimer present in the system can be utilized effectively and resultantly the yield of methionine is improved, the accumulation of impurities and colored substances in the reaction system is avoided, and methionine and potassium bicarbonate can be recovered easily and with good efficiency. Thus, the present invention is of a great industrial value.
- The process according to the invention is suited to increase the yield of the final end product methionine during a process for producing methionine. Due to significantly shorter reaction times (residence times of from 20 s to 200 s) the facilities consisting of special materials, can be constructed smaller, making the process most economic.
- It should be noted, that the hydrolysis (step (d)) of the present invention can be carried out without any addition of a solvent. Furthermore, the hydrolysis of the present invention can be carried out directly with the methionine-mother liquor as starting material. The reaction is catalyzed by either acid or base. Suitable catalyzation can be achieved by adding KOH to adjust the pH to values about 14. Within the claimed temperature and pressure ranges, there occur no bothering side products during the hydrolysis reaction in view of the final carbonization reaction.
-
-
Figure 1 shows a flow chart of the laboratory facility for the embodiment shown in Example 1 below. - The present invention is described in detail below with reference to Examples.
- As to the description of Example 1, please refer also to
Figure 1 . InFigure 1 the used numbers have the following meanings: - 101: glass container
- 102: HPLC pump
- 103: coiled tubing reactor
- 104: cryostat device
- 105: washing bottle
- The reactant solution is suck from the
glass container 101 by theHPLC pump 102. The volume flow is regulated by the number of rotations of the HPLC pump (FIC 102.1). The pressure at the pressure side of the pump is regulated by the pressure control valve (PIC S+ 102.2). An interlock (S+) stops the pump, if the pressure exceeds 40 MPa. - At the pressure side of the pump the starting mixture flows in a 3x1 mm capillary into the coiled
tubing reactor 103. The coiled tubing reactor consists of 6 m capillary of 3x1 mm, wrapped up a tube with an outer diameter of 168 mm filled with isolation material. The capillary wrapped up this tube is incorporated in a heat sleeve with a nominal power of 2 kW. In the hot section between the wrapped capillary and the heat sleeve there are two thermocouples (TI 103.1 and 103.2), one of which serves as over-temperature safety device (TI S+ 103.2). - Downstream the reactor a T-piece can be found, in which a thermocouple is screwed in (TIC 103.3). Therewith the temperature of the solution at the outlet of the
reactor 103 is measured. This measured value is the actual value of the temperature control. For control a further thermocouple (TI 103.4) can be found at the outlet of the reactor, which is fixed outside the capillary. Subsequently the capillary passes a cryostat device, thus the product solution is cooled to about 50°C. - The pressure of the whole facility is shown by the pressure gauge downstream the cryostat device (PI 104.1). The reactant solution is set free by the pressure control valve and collected by the
empty washing bottle 105. -
- Where [met - met] is the concentration of methionyl - methionine at the inlet and outlet of the laboratory facility, respectively.
Table 1 Conversion Rates achieved with Example 1 Temperature Residence time Conversion [°C] [s] [%] 223 24 21 223 24 29 223 32 34 223 39 38 239 18 38 239 24 40 239 31 47 239 38 58 239 60 63 239 107 77 239 157 83 254 18 48 254 23 62 254 30 64 254 37 75
Claims (6)
- A process for producing methionine which comprises the steps of:a) adding at least one compound selected from potassium carbonate, potassium bicarbonate and potassium hydroxide to a solution containing 5- (β-methylmercaptoethyl)hydantoin to hydrolyze the 5- (β-methylmercaptoethyl)hydantoin to obtain a solution containing methionine,b) saturating the solution containing methionine with carbon dioxide to precipitate the methionine, and separating the precipitated methionine while leaving a first filtrate behind,c) dividing the first filtrate into a first part and a second part returning the first part to step (a), and transferring the second part to step (d), wherein the first part of the first filtrate can be absent,d) heating the second part of the first filtrate to a temperature from 210°C to 280°C for a residence time between 20 and 200 seconds and at a pressure above the vapor pressure of the water at the temperature employed, and saturating the heat-treated filtrate with carbon dioxide to precipitate the methionine and potassium bicarbonate, and separating the precipitated methionine and potassium bicarbonate while leaving a second filtrate behind, ande) discharging the second filtrate or returning it to step (a).
- Process according to claim 1, wherein the temperature is from 220°C to 280°C.
- Process according to claims 1 to 2, wherein the temperature is from 220°C to 260°C.
- Process according to any of the preceding claims, wherein the residence times are between 20 and 100 s.
- Process according to any of the preceding claims, wherein the used starting material in step d) is the methionine-mother liquor.
- Process according to any of the preceding claims, wherein step d) is carried out in the absence of a solvent.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES04003353T ES2365849T3 (en) | 2004-02-14 | 2004-02-14 | PROCEDURE TO PRODUCE METIONIN. |
EP04003353A EP1564208B1 (en) | 2004-02-14 | 2004-02-14 | Process for producing methionine |
AT04003353T ATE509908T1 (en) | 2004-02-14 | 2004-02-14 | METHION FOR PRODUCING METHIONINE |
KR1020050011355A KR101149143B1 (en) | 2004-02-14 | 2005-02-07 | Process for producing methionine |
US11/054,424 US7119228B2 (en) | 2004-02-14 | 2005-02-10 | Process for producing methionine |
RU2005103732/04A RU2382768C2 (en) | 2004-02-14 | 2005-02-14 | Method of producing methionine |
SG200500794A SG119263A1 (en) | 2004-02-14 | 2005-02-14 | Process for producing methionine |
BR0500394-6A BRPI0500394A (en) | 2004-02-14 | 2005-02-14 | Process for methionine production |
JP2005036873A JP4939758B2 (en) | 2004-02-14 | 2005-02-14 | Method for producing methionine |
CNB2005100090013A CN100410238C (en) | 2004-02-14 | 2005-02-16 | Process for producing methionine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04003353A EP1564208B1 (en) | 2004-02-14 | 2004-02-14 | Process for producing methionine |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1564208A1 EP1564208A1 (en) | 2005-08-17 |
EP1564208B1 true EP1564208B1 (en) | 2011-05-18 |
Family
ID=34684695
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04003353A Expired - Lifetime EP1564208B1 (en) | 2004-02-14 | 2004-02-14 | Process for producing methionine |
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US (1) | US7119228B2 (en) |
EP (1) | EP1564208B1 (en) |
JP (1) | JP4939758B2 (en) |
KR (1) | KR101149143B1 (en) |
CN (1) | CN100410238C (en) |
AT (1) | ATE509908T1 (en) |
BR (1) | BRPI0500394A (en) |
ES (1) | ES2365849T3 (en) |
RU (1) | RU2382768C2 (en) |
SG (1) | SG119263A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105053577B (en) * | 2008-10-17 | 2019-05-07 | 赢创德固赛有限公司 | The preparation and use of the methionyl methionine of feed addictive as fish and shellfish |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009292796A (en) * | 2008-06-09 | 2009-12-17 | Sumitomo Chemical Co Ltd | Method for producing methionine |
JP2009292795A (en) * | 2008-06-09 | 2009-12-17 | Sumitomo Chemical Co Ltd | Method for producing methionine |
BR112013018092B1 (en) | 2011-02-23 | 2021-04-27 | Evonik Operations Gmbh | METHOD FOR PRODUCTION OF 2-HYDROXY-4- (METHYLTHIUM) BUTANE NITRILLA FROM 3- (Methylthio) PROPANAL AND HYDROGEN CYANIDE AND USE OF A REACTION PRODUCT CONTAINING MMP-CYANIDRINE |
JP2012201672A (en) * | 2011-03-28 | 2012-10-22 | Sumitomo Chemical Co Ltd | Process for producing methionine |
DE102011081828A1 (en) | 2011-08-30 | 2013-02-28 | Evonik Degussa Gmbh | Process for the reaction of methylmercaptopropionaldehyde from crude acrolein and crude methylmercaptan |
EP2750775B1 (en) | 2011-08-30 | 2020-12-09 | Evonik Operations GmbH | Method for producing a methionine salt |
CN102796033B (en) * | 2012-09-03 | 2014-02-26 | 浙江新和成股份有限公司 | Method for preparing clean D,L-methionine |
EP2848607A1 (en) | 2013-09-17 | 2015-03-18 | Evonik Industries AG | Method for extracting methionine |
CN105296557A (en) * | 2015-10-31 | 2016-02-03 | 高大元 | Synthesis method of D, L-alpha-methionine calcium |
SG11201811497PA (en) | 2016-06-27 | 2019-01-30 | Evonik Degussa Gmbh | Dipeptide-containing granular material |
CN110678446B (en) | 2017-05-15 | 2021-11-26 | 赢创运营有限公司 | Method for producing methionine |
EP3431465A1 (en) | 2017-07-21 | 2019-01-23 | Evonik Degussa GmbH | Process for preparing methionine |
EP3404018A1 (en) | 2017-05-15 | 2018-11-21 | Evonik Degussa GmbH | Process for preparing methionine |
EP3406593A1 (en) | 2017-05-24 | 2018-11-28 | Evonik Degussa GmbH | Method for manufacturing methionine |
EP3461803A1 (en) * | 2017-10-02 | 2019-04-03 | Evonik Degussa GmbH | Method for the production of granules containing dipeptide |
CN112661683A (en) * | 2020-12-22 | 2021-04-16 | 宁夏紫光天化蛋氨酸有限责任公司 | DL-methionine production method without discharged wastewater |
CN114213293A (en) * | 2021-12-23 | 2022-03-22 | 天宝动物营养科技股份有限公司 | Preparation method of methionine |
Family Cites Families (12)
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US4069251A (en) * | 1969-02-08 | 1978-01-17 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Continuous process for the manufacture of methionine |
DE2421167C3 (en) * | 1974-05-02 | 1978-05-11 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the production of methionine and potassium hydrogen carbonate from the circulating mother liquors of the potassium carbonate methionine process |
US4461007A (en) * | 1982-01-08 | 1984-07-17 | Xerox Corporation | Injection lasers with short active regions |
FR2601674B1 (en) * | 1986-07-17 | 1988-09-23 | Aec Chim Organ Biolog | PROCESS FOR THE PREPARATION OF AN AQUEOUS SOLUTION OF METHIONINE SODIUM SALT |
JP3206103B2 (en) * | 1992-05-22 | 2001-09-04 | 住友化学工業株式会社 | Method for producing methionine |
DE19547236A1 (en) * | 1995-12-18 | 1997-07-03 | Degussa | Process for the preparation of D, L-methionine or its salt |
JP3620243B2 (en) * | 1996-10-31 | 2005-02-16 | 住友化学株式会社 | Method for producing methionine |
ES2166036T3 (en) * | 1996-10-31 | 2002-04-01 | Sumitomo Chemical Co | PROCEDURE TO PRODUCE METIONIN. |
JP3292119B2 (en) * | 1997-11-26 | 2002-06-17 | 住友化学工業株式会社 | Method for producing methionine |
CN1178909C (en) * | 1999-05-21 | 2004-12-08 | 住友化学工业株式会社 | Prepn. of methionine |
JP3624243B2 (en) | 2000-08-21 | 2005-03-02 | 独立行政法人産業技術総合研究所 | Continuous protein degradation method |
JP4338524B2 (en) * | 2001-11-29 | 2009-10-07 | 日本曹達株式会社 | Method for producing methionine |
-
2004
- 2004-02-14 AT AT04003353T patent/ATE509908T1/en not_active IP Right Cessation
- 2004-02-14 EP EP04003353A patent/EP1564208B1/en not_active Expired - Lifetime
- 2004-02-14 ES ES04003353T patent/ES2365849T3/en not_active Expired - Lifetime
-
2005
- 2005-02-07 KR KR1020050011355A patent/KR101149143B1/en not_active IP Right Cessation
- 2005-02-10 US US11/054,424 patent/US7119228B2/en not_active Expired - Fee Related
- 2005-02-14 SG SG200500794A patent/SG119263A1/en unknown
- 2005-02-14 RU RU2005103732/04A patent/RU2382768C2/en not_active IP Right Cessation
- 2005-02-14 BR BR0500394-6A patent/BRPI0500394A/en not_active IP Right Cessation
- 2005-02-14 JP JP2005036873A patent/JP4939758B2/en not_active Expired - Fee Related
- 2005-02-16 CN CNB2005100090013A patent/CN100410238C/en not_active Expired - Fee Related
Cited By (1)
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CN105053577B (en) * | 2008-10-17 | 2019-05-07 | 赢创德固赛有限公司 | The preparation and use of the methionyl methionine of feed addictive as fish and shellfish |
Also Published As
Publication number | Publication date |
---|---|
JP4939758B2 (en) | 2012-05-30 |
CN1680311A (en) | 2005-10-12 |
EP1564208A1 (en) | 2005-08-17 |
BRPI0500394A (en) | 2005-12-06 |
KR20060041832A (en) | 2006-05-12 |
US20050267314A1 (en) | 2005-12-01 |
SG119263A1 (en) | 2006-02-28 |
ATE509908T1 (en) | 2011-06-15 |
KR101149143B1 (en) | 2012-05-25 |
RU2382768C2 (en) | 2010-02-27 |
RU2005103732A (en) | 2006-07-20 |
JP2005225882A (en) | 2005-08-25 |
ES2365849T3 (en) | 2011-10-11 |
US7119228B2 (en) | 2006-10-10 |
CN100410238C (en) | 2008-08-13 |
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